アリルアニオン・アリルカチオンの13C NMR化学シフト (Me4Si基準，ppm)13C NMR chemical shifts of allyl cation/anions

(G. Olah et al., J. Am. Chem. Soc., 100, 4347 (1978))

Ref.

124

133

26

Ref.

115135

19

Ref. 115

13538

- 両端の等価性，両端と中心炭素の環境の違い，アニオン・カチオンの化学シフト- Equivalence of two termini. Difference between terminal and center. Chemical shift of

cations/anions

HOMO (-9.13 eV)

One of other occupied MOs (-13.49 eV)

Styrene C6H5-CH=CH2

Molecular orbitals with p-character

HOMO (-9.17 eV)

One of other occupied MOs (-14.70 eV)

Phenol C6H5-OH

- Oxygen is involved in p-system

Molecular orbitals with p-character

HOMO (-9.44 eV)

One of other occupied MOs (-14.57 eV)

Toluene C6H5-CH3

Molecular orbitals with p-character

- Methyl group is also involved in p-system !?

HOMO (-10.10 eV)

One of other occupied MOs (-14.57 eV)

propene CH3-CH=CH2

… likewise

HOMO (-9.14 eV)

One of other occupied MOs (-15.47 eV)

2,3-dimethylbut-2-ene (CH3)2C=C(CH3)2

p-system is extended to outer alkyl group!

2-methylpropene (CH3)C=CH2

180 190

but-1-ene CH3CH2CH=CH2

170 180

3.0

1.5

190

4.0

3.5

2,3-dimethylbut-2-ene (CH3)2C=C(CH3)2

190 210 230

4.0

2.0

置換アルケンのUV/visスペクトル UV/vis spectra of substituted alkenes

アルキルカチオン – 空の2pz軌道への電子供与による非局在化

alkyl cations – delocalization by donation of electrons

toward unoccupied 2pz orbital.

methane -13.01 kcal/mol

ethane -18.13 kcal/mol

methyl cation 256.55 kcal/mol

ethyl cation 222.56 kcal/mol

propane -23.62 kcal/mol 2-propyl cation 197.25 kcal/mol

cf. 1-propyl cation 214.36 kcal/mol

HClの解離と水和エネルギー

HCl(aq)

H+(aq) + Cl-(aq)40 kJ/mol

H・ (g) + Cl ・(g)

427 kJ/mol

HCl(g)

5 kJ/mol

Cl-(aq)

322 kJ/mol

H+(g) + Cl-(g)

1347 kJ/mol

H+(aq)

1098 kJ/molH3O

+(g)

686 kJ/mol

H+(g) + H2O (g)

アンモニアのHOMO 水のHOMO

塩基性とＨＯＭＯのレベル

C OHCH3

CH3

H3CH

H

EtOH

H2O

MeOH

PhOH

CH3 C CH3

O H

CH3 C OH

O H

CH3 C OH

O

CH3 C CH3

O

CH3 C OCH3

O

CH4

PhCH3

PhNH2

HF

HCl

HI

HNO3

H2SO4

NH4

H3O

EtNH2

NH3

CH2H2C

CHHC

CHH2C CH3

CH3 NO2

CH3COCH2COOCH3

iPr2NH

HN

H2N

Et3NH

Et2NH2

40

30

20

10

0

-10

50

EtNH3

PhNH3

MeOH2

EtOH2

水中での値に換算したpKa値

49

41

35

27

25

20

18

16

15.7

15

10

4.8

3.2

-1.4

-5.2

-7

-10

10.7

9.2

4.6

-1.7

-2.2

-2.4

-6.0

-7.2

16

酸として弱い

酸として強い

（共役塩基が）塩基として強い

（共役塩基が）塩基として弱い

36

有機化学１資料

44

25

44

10

14

36

5

-4

10.8

11

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Structure & Reactivity in Organic, Biological and Inorganic Chemistry by Chris Schaller is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported License.